Methods and systems for recovering rhenium from a copper leach

ABSTRACT

Various embodiments provide new methods of rhenium recovery. The methods can include subjecting a metal-bearing solution to an activated carbon bed, and adsorbing rhenium onto the activated carbon. The methods can also include heating a basic aqueous elution solution and eluting the rhenium from the activated carbon with the heated elution solution. The methods can also incorporate an ion exchange as a rhenium recovery apparatus.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority to U.S. patentapplication Ser. No. 13/588,448 filed Aug. 17, 2012, entitled “Methodsand Systems for Recovering Rhenium from a Copper Leach,” which is adivisional of and claims priority to U.S. patent application Ser. No.12/424,863, filed Apr. 16, 2009 entitled “Methods and Systems forRecovering Rhenium from a Copper Leach,” which are both herebyincorporated by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates generally to the recovery of rhenium andrelates more specifically to the recovery of rhenium from a copperleach.

BACKGROUND

Rhenium was the last naturally occurring element to be discovered andthe last element discovered having a stable isotope. Rhenium istypically recovered as a byproduct of molybdenum refinement. Sincerecovery of rhenium from molybdenite is difficult and the concentrationsof rhenium in molybdenite are very low, typically from about 0.002% toabout 0.02%, rhenium is one of the most expensive metals available incommodity markets. Rhenium has several characteristics that make itunique, such as, for example, the second highest melting point amongstmetals, amongst the densest metals, a super conductor, and the greatestnumber of oxidation states of any element. Industrial applicationsinclude the use of rhenium in catalysts, electronics, thermocouples,high temperature turbine blades, and photoflash devices.

Rhenium may be extracted from ores that contain copper and molybdenum.Common practice for leaching copper from low-grade copper ore is toplace the ore in a heap leach pad and leach the ore with dilute sulfuricacid solution. The resulting copper-bearing solution is typicallyconcentrated via solvent extraction and/or electrowon to produce purecopper cathode. Typically, the copper-bearing solution has less than onepart per million of dissolved rhenium and may contain significantamounts of other metals in the copper-bearing solution. Recovery ofrhenium from the copper-bearing solution is not economically feasibleand hence rhenium is, along with other metal values, typically notrecovered from the copper-bearing solution before the electrowinningstage.

Generally, rhenium is recovered as a result of the molybdenite roastingto produce molybdenum. The acid blow-down from the molybdenite roastingoff-gas contains concentrations of rhenium which are much higher thanthe concentrations of rhenium in the copper-bearing solution. Inaddition, the acid blow-down stream does not contain the metal valuessuch as copper or molybdenum since they have already been recoveredupstream, and this allows rhenium to be recovered from the acidblow-down stream by ion exchange, solvent extraction and/orcrystallization.

Since the demand for rhenium continues to increase on a year-by-yearbasis, new methods for rhenium recovery from sources other thanmolybdenum roasting processes are needed.

SUMMARY

In accordance with various embodiments, the present invention providesnew methods of rhenium recovery. The methods can include subjecting acopper-bearing solution to an activated carbon bed, and adsorbingrhenium onto the activated carbon. The methods can also include heatinga basic aqueous elution solution and eluting the rhenium from theactivated carbon with the heated elution solution.

In addition, various embodiments of the present invention providesystems for the recovery of rhenium from copper leach heap. Systems caninclude an effluent entry in communication with at least one activatedcarbon bed and an effluent exit in communication with the activatedcarbon bed and distal to the effluent entry. In such systems, effluententry can feed a copper-bearing solution comprising a rhenium metalvalue through the activated carbon bed while the effluent exit allowsthe remainder of the copper-bearing solution to exit the activatedcarbon bed after allowing the rhenium to adsorb onto the activatedcarbon. In an exemplary embodiment of the present invention, the atleast one activated carbon bed can be a plurality of activated carbonbeds connected to each other in series. Various embodiments of thesystems can include an elution stream controllably in communication withthe at least one bed of activated carbon. In an exemplary embodiment,the systems can include an eluate port controllably in communicationwith the bed of activated carbon and the eluate exit can be operable toremove a rhenium stream.

Further areas of applicability will become apparent from the descriptionprovided herein. It should be understood that the description and thespecific examples are intended for purposes of illustration only, andare not intended to limit the scope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.The present invention will become more fully understood from thedetailed description and the accompanying drawings wherein:

FIG. 1 is a block diagram illustrating a rhenium recovery process,according to various embodiments of the present invention;

FIG. 2 is a block diagram illustrating a rhenium recovery system,according to various embodiments of the present invention;

FIG. 3 is a block diagram illustrating a first exemplary process forrecovering rhenium and a second metal value from a metal-bearingmaterial, according to various embodiments of the present invention;

FIG. 4 is a block diagram illustrating a second exemplary process forrecovering rhenium and a second metal value from a metal-bearingmaterial, according to various embodiments of the present invention;

FIG. 5 is a block diagram illustrating a third exemplary process forrecovering rhenium and a second metal value from a metal-bearingmaterial, according to various embodiments of the present invention;

FIG. 6 is a block diagram illustrating a method for recovering rheniumaccording to various embodiments of the present invention; and

FIG. 7 is a flow diagram further illustrating a plant scale process forrecovering rhenium, according to various embodiments of the presentinvention.

DETAILED DESCRIPTION

The following description is merely exemplary in nature, and is notintended to limit the present invention, its applications, or its uses.It should be understood that throughout the drawings, correspondingreference numerals indicate like or corresponding parts and/or features.The descriptions' specific examples indicated in various embodiments ofthe present invention are intended for purposes of illustration only andare not intended to limit the scope of the invention disclosed herein.Moreover, recitation of multiple embodiments having stated features isnot intended to exclude other embodiments having additional features orother embodiments incorporating different combinations of the statedfeatures.

Various embodiments of the present invention are an improvement to therecovery of rhenium from ore bodies comprising copper and molybdenum. Invarious embodiments, rhenium can be recovered from a copper-bearingstream produced from copper leaching. Since the world demand for rheniumcontinues to increase, improvements are needed to recover rhenium fromnew sources. Since copper each solutions can comprise dissolved rhenium,the present invention provides methods and systems for the recovery ofrhenium from such solutions.

With reference to FIG. 1, rhenium recovery process 10 is illustratedaccording to various embodiments of the present invention, Rheniumrecovery process 10 can comprise metal bearing stream 22, stationaryphase 23, elution solution 25, and remainder solution 24. Metal-bearingstream 22 can comprise one or more metal values. In an exemplaryembodiment, metal-bearing stream 22 comprises rhenium. In variousembodiments, metal-bearing stream 22 can be a product resulting from ametal leaching process, such as, for example, a pregnant leach solution.Generally, metal-bearing stream 22 can be acidic, and may comprisesulfuric acid. In some aspects of the present invention, metal-bearingstream 22 can be a product of a solvent extraction process following ametal leaching process, such as, for example, a raffinate solution. Inother aspect the metal-bearing stream 22 can be the product of leachingprior to solvent extraction, such as, for example, a pregnant leachsolution. In other aspects of the present invention, metal-bearingsolution can be a solution exiting from an electrowinning apparatus,such as, for example, lean electrolyte.

In various embodiments, stationary phase 23 can be any material, whichcan operably adsorb rhenium. In general, any porous material exhibitingadsorption properties due to high surface area is suitable. In anexemplary embodiment, stationary phase 23 can comprise carbon, such as,for example, activated carbon, activated charcoal, and/or activatedcoal. Another example of carbon useful for stationary phase 23 includesa coconut shell activated carbon having a U.S. sieve mesh size of 6×12.Any type or size of activated carbon, such as powder, particle, orgranular sizes may be used in the present invention. The size of theactivated carbon, typically measured in mesh size, can be determined bysuch factors as metal-bearing stream flow rate, activated carbon bedvolume, adsorption capacity, and the like.

In various embodiments, stationary phase 23 can be static or fluidized.In an aspect of the invention, stationary phase 23 can be fluidized inthe flow of metal-bearing stream 22. The fluidized stationary phase 23can be collected in a down stream process, such as, for example, use ofa screen or a sieve. The collected stationary phase 23 can then besubjected to elution solution 25 for recovery of metal value 28. Inanother aspect of the invention, stationary phase 23 can be static in acolumn with a mobile phase, such as metal-bearing stream 22, passingover stationary phase 23 and adsorbing metal value 28 onto stationaryphase 23. Stationary phase 23 containing adsorbed metal value 28 can besubjected to elution solution 25 for recovery of metal value 28.

In various embodiments, remainder solution 24 can comprise metal-bearingstream 22 less material adsorbed on stationary phase 23. In an exemplaryembodiment, remainder solution 24 comprises at least 80% less rheniumthan metal-bearing stream 22, and preferably at least 90% less rhenium,and more preferably at least 95% less rhenium. In an aspect of thepresent invention, remainder solution 24 can be further processed torecover at least one metal value. In an exemplary embodiment, the atleast one metal value is at least one of copper and molybdenum. Inanother aspect of the present invention, remainder solution 24 can becycled for its acid content to any other process in a metal recoverysystem, such as, for example, a leaching process, a conditioningprocess, and/or a solvent extraction process.

In various embodiments, elution solution 25 can comprise any eluate,which can extract metal value 28 off of stationary phase 23. In general,elution solution 25 can be an aqueous solution having a pH greater thanabout 7. In an exemplary embodiment, elution solution 25 can comprise ahydroxide salt in an aqueous solution. For example, a hydroxide salt canbe at least one of sodium hydroxide, ammonium hydroxide, lithiumhydroxide, and potassium hydroxide. In an exemplary embodiment, elutionsolution 25 can be an aqueous solution comprising sodium hydroxide in anamount from about 0.1% to about 10% or preferably an amount from about0.2% to about 5%, or more preferably an amount from about 0.5% to about2.5%. In another exemplary embodiment, elution solution 25 can be anaqueous solution comprising ammonium hydroxide in an amount from about0.1% to about 10% or preferably an amount from about 0.2% to about 5%,or more preferably an amount from about 0.5% to about 2.5%.

With continued reference to FIG. 1, in various embodiments, elutionsolution 25 can be heated to a temperature greater than or equal to 80°C. In an exemplary embodiment, elution solution 25 can be heated to atemperature from about 80° C. to about 130° C., and preferably to atemperature from about 90° C. to about 120° C., and more preferably to atemperature from about 105° C. to about 115° C., and even morepreferably to a temperature from about 108° C. to about 110° C. In anaspect of the invention, as the temperature of elution solution 25 isincreased, the amount of the hydroxide salt in the aqueous solution canbe decreased. As the temperature of elution solution 25 is increased,the elution efficiency increases. In addition, as the temperature ofelution solution 25 is increased, the costs of elution solution 25decrease.

In various embodiments, a method for recovering rhenium can comprisepassing metal-bearing stream 22 through stationary phase 23 andadsorbing a metal value on stationary phase 23. The method can compriseremoving remainder solution 24 from stationary phase 23. The method canfurther comprise recovering a second metal value from remainder solution24. The method can comprise stopping the metal-bearing stream 22 andeluting metal value 28 from stationary phase 23. The method can furthercomprise heating elution solution 25 then eluting metal value 28 fromstationary phase 23. In an exemplary embodiment, metal value 28 isrhenium.

Now referring to FIG. 2, rhenium recovery system 20 is illustratedaccording to various embodiments of the present invention. Metal-bearingmaterial 212 may be an ore, a concentrate, or any other material fromwhich metal values may be recovered. Metal values such as, for example,copper, gold, silver, zinc, platinum group metals, nickel, cobalt,molybdenum, rhenium, uranium, rare earth metals, and the like may berecovered from metal-bearing material 212 in accordance with variousembodiments of the present invention. Various aspects and embodiments ofthe present invention, however, prove especially advantageous inconnection with the recovery of copper from copper sulfide concentratesand/or ores, such as, for example, chalcopyrite (CuFeS₂), chalcocite(Cu₂S), bornite (Cu₅FeS), covellite (CuS), enargite (Cu₃AsS₄), digenite(Cu₉S₅), and/or mixtures thereof. Thus, in various embodiments,metal-bearing material 212 is a copper ore or concentrate, and in anexemplary embodiment, metal-bearing material 212 is a copper sulfide oreor concentrate.

In various embodiments, processed metal-bearing material 213 maycomprise metal-bearing material 212 prepared for metal recovery process20 in any manner that enables the conditions of processed metal-bearingmaterial 213 to be suitable for a chosen processing method, as suchconditions may affect the overall effectiveness and efficiency ofprocessing operations. Desired composition and component concentrationparameters may be achieved through a variety of chemical and/or physicalprocessing stages, the choice of which will depend upon the operatingparameters of the chosen processing scheme, equipment cost and materialspecifications. For example, metal-bearing material 212 may undergocomminution, flotation, blending, and/or slurry formation, as well aschemical and/or physical conditioning to produce processed metal-bearingmaterial 213. In an exemplary embodiment, processed metal-bearingmaterial 213 is a concentrate.

With continued reference to FIG. 2, after metal-bearing material 212 hasbeen suitably prepared, processed metal-bearing material 213 issubjected to reactive processing 214 to put a metal value or metalvalues in processed metal-bearing material 213 in a condition for latermetal recovery steps, namely metal recovery 218. For example, exemplarysuitable processes include reactive processes that tend to liberate thedesired metal value or metal values from the metal-bearing material 212.In accordance with an exemplary embodiment of the present invention,reactive processing 214 may comprise leaching. Leaching can be anymethod, process, or system that enables a metal value to be leached fromprocessed metal-bearing material 213. Typically, leaching utilizes acidto each a metal value from processed metal-bearing material 213. Forexample, leaching can employ a leaching apparatus, such as, for example,a heap leach, a vat leach, a tank leach, a pad leach, a leach vessel orany other leaching technology useful for leaching a metal value fromprocessed metal-bearing material 213.

In accordance with various embodiments, leaching may be conducted at anysuitable pressure, temperature, and/or oxygen content. Leaching canemploy one of a high temperature, a medium temperature, or a lowtemperature, combined with one of high pressure, or atmosphericpressure. Leaching may utilize conventional atmospheric or pressureleaching, for example, but not limited to, low, medium or hightemperature pressure leaching. As used herein, the term “pressureleaching” refers to a metal recovery process in which material iscontacted with an acidic solution and oxygen under conditions ofelevated temperature and pressure. Medium or high temperature pressureleaching processes for chalcopyrite are generally thought of as thoseprocesses operating at temperatures from about 120° C. to about 190° C.or up to about 250° C. In accordance with various embodiments of thepresent invention, reactive processing 214 may comprise any type ofreactive process to put a metal value or values in processedmetal-bearing material 213 in a condition to be subjected to later metalrecovery steps.

In various embodiments, reactive processing 214 provides a metal-bearingslurry 215 for conditioning 216. In various embodiments, conditioning216 can be, for example, but is not limited to, a solid liquid phaseseparation step, an additional each step, a pH adjustment step, adilution step, a concentration step, a metal precipitation step, afiltering step, a settling step, and the like, as well as combinationsthereof. In an exemplary embodiment, conditioning 216 can be a solidliquid phase separation step configured to yield a metal-bearingsolution 217 and a metal-bearing solid.

In other various embodiments, conditioning 216 may be one or moreleaching steps. For example, conditioning 216 may be any method,process, or system that further prepares metal-bearing material 212 forrecovery. In various embodiments, conditioning 216 utilizes acid toleach a metal value from a metal-bearing material. For example,conditioning 216 may employ a leaching apparatus such as, for example, aheap leach, a vat leach, a tank leach, a pad leach, a leach vessel orany other leaching technology useful for leaching a metal value from ametal-bearing material.

In accordance with various embodiments, conditioning 216 may be a leachprocess conducted at any suitable pressure, temperature, and/or oxygencontent. In such embodiments, conditioning 216 may employ one of a hightemperature, a medium temperature, or a low temperature, combined withone of high pressure, or atmospheric pressure. Conditioning 216 mayutilize conventional atmospheric or pressure leaching, for example, butnot limited to, low, medium or high temperature pressure leaching.Medium or high temperature pressure leaching processes for chalcopyriteare generally thought of as those processes operating at temperaturesfrom about 120° to about 190° C. or up to about 250° C.

In various embodiments, conditioning 216 may comprise dilution,settling, filtration, solution/solvent extraction, ion exchange, pHadjustment, chemical adjustment, purification, concentration, screening,and size separation. In various embodiments, conditioning 216 is a hightemperature, high pressure leach. In other embodiments, conditioning 216is an atmospheric leach. In further embodiments, conditioning 216 is asolid liquid phase separation. In still further embodiments,conditioning 216 is a settling/filtration step. In various embodiments,conditioning 216 produces metal-bearing solution 217.

With further reference to FIG. 2, in various embodiments, metal-bearingsolution 217 may be passed through stationary phase 23. As describedabove, metal value 28 can be adsorbed onto stationary phase 23. Aremainder solution 24 can be removed from stationary phase 23. Metalvalue 28 can be eluted off stationary phase 23 with elution solution 25,Elution solution 25 can be heated as described herein. In a preferableembodiment, metal value 28 is rhenium.

In an exemplary embodiment, stationary phase 23 can be combined withmetal-bearing solution 217 to create a slurry. In this exemplaryembodiment, stationary phase 23 is fluidized in the slurry. A coursecarbon powder can be advantageous for use as stationary phase 23. Metalvalue 28 can be adsorbed on to stationary phase 23. Fluidized stationaryphase 23 can be collected by use of a screen or a sieve. Metal value 28can be eluted off stationary phase 23 with elution solution 25 asdescribed herein.

In various embodiments, remainder solution 24 may be subjected to metalrecovery 218 to yield metal value 220. In exemplary embodiments, metalrecovery 218 can comprise electrowinning remainder solution 24 to yieldrecovered metal value 220 as a cathode. In one exemplary embodiment,metal recovery 218 may be configured to employ conventionalelectrowinning processes and include a solvent extraction step, an ionexchange step, an ion selective membrane, a solution recirculation step,and/or a concentration step. In one preferred embodiment, metal recovery218 may be configured to subject remainder solution 24 to a solventextraction step to yield a rich electrolyte solution, which may besubject to an electrowinning circuit to recover a desired metal value220. In another exemplary embodiment, metal recovery 218 may beconfigured to employ direct electrowinning processes without the use ofa solvent extraction step, an ion exchange step, an ion selectivemembrane, a solution recirculation step, and/or a concentration step. Inanother preferred embodiment, metal recovery 218 may be configured tofeed remainder solution 24 directly into an electrowinning circuit torecover a desired metal value 220. In an especially preferredembodiment, metal value 220 is copper.

Turning to FIG. 3, a first exemplary process 30 for recovering rheniumand a second metal value from a metal-bearing material 212 isillustrated according to various embodiments of the present invention.After metal-bearing material 212 has been suitably prepared, processedmetal-bearing material 213 is subjected to reactive processing 214 toput a metal value or metal values in processed metal-bearing material213 in a condition for later metal recovery steps, namely first metalrecovery 225 and second metal recovery 218. In accordance with anexemplary embodiment of the present invention, reactive processing 214comprises a leaching process.

In various embodiments, reactive processing 214 provides metal-bearingslurry 215 for conditioning 216. In an exemplary embodiment,conditioning 216 can be a solid liquid phase separation step configuredto yield metal-bearing solution 217 and a metal-bearing solid. Invarious embodiments, metal-bearing solution 217 is subjected to firstmetal recovery 225 to recover first metal value 28. First metal recovery225 comprises valve 222 in communication with conditioning 216, andfirst stationary phase 23A and second stationary phase 238 connected inparallel with valve 222. Valve 222 can control flow of metal-bearingsolution 217 to either first stationary phase 23A or second stationaryphase 23B. In various embodiments, metal-bearing solution 217 passesthrough a first stationary phase 23A until first stationary phase 23A isloaded with metal value 28 to near capacity. Then valve 222 switches theflow of metal-bearing solution 217 to pass through second stationaryphase 23B. After valve 222 switches, elution solution 25A can be passedthrough stationary phase 23A to elute metal value 28. When secondstationary phase 23B is loaded with metal value 28 to near capacity,valve 222 switches flow of metal-bearing solution 217 back to stationaryphase 23A. After valve 222 switches the second time, elution solution25B can be passed through stationary phase 23B to elute metal value 28.

In various embodiments, remainder solution 24 may be subjected to metalrecovery 218 to yield metal value 220. In exemplary embodiments, metalrecovery 218 can comprise electrowinning remainder solution 24 to yieldrecovered metal value 220 as a cathode. In a preferred embodiment, metalrecovery 218 may be configured to feed remainder solution 24 directlyinto an electrowinning circuit to recover a desired metal value 220. Inan especially preferred embodiment, metal value 220 is copper.

Moving to FIG. 4, a second exemplary process 40 for recovering rheniumand a second metal value from a metal-bearing material 212 isillustrated according to various embodiments of the present invention.After metal-bearing material 212 has been suitably prepared, processedmetal-bearing material 213 is subjected to reactive processing 214 toput a metal value or metal values in processed metal-bearing material213 in a condition for later metal recovery steps, namely first metalrecovery 225 and second metal recovery 218. In accordance with anexemplary embodiment of the present invention, reactive processing 214comprises a leaching process.

In various embodiments, reactive processing 214 provides metal-bearingslurry 215 for conditioning 216. In an exemplary embodiment,conditioning 216 can be a solid liquid phase separation step configuredto yield metal-bearing solution 217 and a metal-bearing solid. Invarious embodiments, metal-bearing solution 217 is subjected to firstmetal recovery 225 to recover first metal value 28. First metal recovery225 comprises valve 222 in communication with conditioning 216, andfirst stationary phase 23A and second stationary phase 23B connected inparallel with valve 222. Valve 222 can control flow of metal-bearingsolution 217 to either first stationary phase 23A or second stationaryphase 23B. In various embodiments, metal-bearing solution 217 passesthrough a first stationary phase 23A until first stationary phase 23A isloaded with metal value 28 to near capacity. Then valve 222 switches theflow of metal-bearing solution 217 to pass through second stationaryphase 23B. After valve 222 switches, elution solution 25A can be passedthrough stationary phase 23A to elute metal value 28. When secondstationary phase 23B is loaded with metal value 28 to near capacity,valve 222 switches flow of metal-bearing solution 217 back to stationaryphase 23A. After the valve 222 switches the second time, elutionsolution 258 can be passed through stationary phase 238 to elute metalvalue 28.

In various embodiments, remainder solution 24 can be subjected tosolvent extraction 230. In accordance with various aspects of thisembodiment of the present invention, solvent extraction 230 can beconfigured to selectively extract a metal value, such as, for examplecopper. During solvent extraction 230, a metal value, such as, forexample copper, from metal-bearing solution may be loaded selectivelyonto an organic chelating agent, for example, an aldoxime/ketoximeblend, resulting in a metal value containing organic stream and araffinate solution. In various embodiments, the metal value containingorganic stream may comprise a copper compound. Solvent extraction 230can be configured to select for a metal value, such as copper by theselection of an appropriate mixture of ketoximes and/or aldoximes.Solvent extraction 230 can produce a raffinate solution and a richelectrolyte 32. In various embodiments, solvent extraction 230 can yielda rich electrolyte 32 comprising a metal value.

Raffinate from solvent extraction 230 advantageously may be used in anumber of ways. For example, all or a portion of raffinate may berecycled to reactive processing 214, such as, for example to aid withtemperature control or solution balancing, or it may be used in otherleaching operations, or it may be used for any combination thereof. Theuse of raffinate in reactive processing 214 may be beneficial becausethe acid values contained in raffinate may act to optimize the potentialfor leaching oxide and/or sulfide ores that commonly dominate heapleaching operations. It should be appreciated that the properties ofraffinate, such as component concentrations, may be adjusted inaccordance with the desired use of raffinate.

In various embodiments, rich electrolyte 32 may be subjected to metalrecovery 218 to yield metal value 220. In exemplary embodiments, metalrecovery 218 can comprise electrowinning rich electrolyte 32 to yieldrecovered metal value 220 as a cathode. In a preferred embodiment, metalrecovery 218 may be configured to feed rich electrolyte 32 directly intoan electrowinning circuit to recover a desired metal value 220. In anespecially preferred embodiment, metal value 220 is copper.

With reference to FIG. 5, a third exemplary process 50 for recoveringrhenium and a second metal value from a metal-bearing material 212 isillustrated according to various embodiments of the present invention.After metal-bearing material 212 has been suitably prepared, processedmetal-bearing material 213 is subjected to reactive processing 214 toput a metal value or metal values in processed metal-bearing material213 in a condition for later metal recovery 218. In accordance with anexemplary embodiment of the present invention, reactive processing 214comprises a leaching process. In various embodiments, reactiveprocessing 214 provides metal-bearing slurry 215 for conditioning 216.

With further reference to FIG. 5, in various embodiments,metal-raffinate 36 may be passed through stationary phase 23. Asdescribed above, metal value 28 can be adsorbed onto stationary phase23. A remainder solution 24 can be removed from stationary phase 23.Metal value 28 can be eluted off stationary phase 23 with elutionsolution 25. Elution solution 25 can be heated as described above. In apreferable embodiment, metal value 28 is rhenium.

With reference to FIG. 6, an exemplary method 60 for recovery of rheniumis illustrated according to various embodiments of the presentinvention. A column comprising a stationary phase, such as activatedcarbon 302, can be placed in communication with a rhenium-rich pregnantleach solution 304 (“Re-rich PLS 304”). In an exemplary embodiment,Re-rich PLS 304 can comprise rhenium and copper. Re-rich PLS 304 canoriginate from an active copper leach or a stockpile copper leach, forexample, residing in a pond or a pit. In an exemplary embodiment,Re-rich PLS 304 can be an acid blow-down stream or leach of molybdeniteroaster flue fumes and dusts. In another exemplary embodiment, Re-richPLS 304 can be a raffinate stream. One skilled in the art willappreciate that any solution comprising rhenium, in any concentration,is suitable for use herewith. For example, solutions containing more orless than 1 mg/L rhenium, even in the presence of iron, copper,molybdenum, vanadium and other metals, are suitable for use herewith.One skilled in the art wiH further appreciate that flow through aplurality of columns, in series, in parallel, or in any otherarrangement, is within the scope of this disclosure.

Rhenium can be adsorbed 306 onto activated carbon 302 of the column anda rhenium-lean pregnant leach solution 308 can exit from the column. Therhenium-loaded column 310 can be placed in communication with elutionsolution 312. Elution solution 312 can be heated 314 to a temperature.In various embodiments, elution solution 312 can comprise any eluate,which can extract rhenium off of the loaded column 310. In general,elution solution 312 can be an aqueous solution having a pH greater thanabout 7.

In an exemplary embodiment, elution solution 312 can comprise ahydroxide salt in an aqueous solution. For example, a hydroxide salt canbe at least one of sodium hydroxide, ammonium hydroxide, lithiumhydroxide, and potassium hydroxide. In an exemplary embodiment, elutionsolution 312 can be an aqueous solution comprising sodium hydroxide inan amount from about 0.1% to about 10% or preferably an amount fromabout 0.2% to about 5%, or more preferably an amount from about 0.5% toabout 2.5%. In another exemplary embodiment, elution solution 312 can bean aqueous solution comprising ammonium hydroxide in an amount fromabout 0.1% to about 10% or preferably an amount from about 0.2% to about5%, or more preferably an amount from about 0.5% to about 2.5%.

In various embodiments, elution solution 312 can be heated 314 to atemperature greater than or equal to 80° C. In an exemplary embodiment,elution solution 312 can be heated 314 to a temperature from about 80°C. to about 130° C., and preferably to a temperature from about 90° C.to about 120° C., and more preferably to a temperature from about 105°C. to about 115° C., and even more preferably to a temperature fromabout 108° C. to about 110° C. In an aspect of the invention, as thetemperature of elution solution 312 is increased 314, the amount of thehydroxide salt in the aqueous solution can be decreased. As thetemperature of elution solution 312 is increased 314, the elutionefficiency increases. In addition, as the temperature of elutionsolution 312 is increased 314, the costs of the elution solution 312decrease.

In various embodiments, rhenium can be eluted 316 from rhenium-loadedcolumn 310 to produce Re-rich aqueous eluate 318. Optionally, thestationary phase of the column can be regenerated 320 and recycled asactivated carbon 302. Optionally, Re-rich eluate 318 can be subjected toa rhenium recovery 322 to produce pure rhenium 326 and Re-lean aqueouseluate 324. Optionally Re-lean eluate 324 can be recycled 328 to elutionsolution 312.

Finally turning to FIG. 7, plant scale process 70 for recovering rheniumis illustrated according to various embodiments of the presentinvention. According to plant scale process 70, rhenium rich PLS 704flows into a first adsorption column 728 containing first partiallyloaded carbon 730 from second adsorption column 732. Any suitableadsorption column may be used with the present invention, for example, atwelve-foot diameter by twelve-foot high adsorption column.

First partially adsorbed rhenium PLS 734 flows from first adsorptioncolumn 728 into second adsorption column 732 containing second partiallyloaded carbon 736 from third adsorption column 738. The amount ofrhenium adsorbed onto second partially loaded carbon 736 can be lessthan that adsorbed onto first partially loaded carbon 730.

Second partially adsorbed rhenium PLS 740 flows from second adsorptioncolumn 732 into third adsorption column 738 containing a third partiallyloaded carbon 742 from a fourth adsorption column 744. The amount ofrhenium adsorbed onto third partially loaded carbon 742 is less thanthat adsorbed onto second partially loaded carbon 736.

Third partially adsorbed rhenium PLS 746 flows from third adsorptioncolumn 738 into fourth adsorption column 744 containing fourth partiallyloaded carbon 748 from fifth adsorption column 750. The amount ofrhenium adsorbed onto fourth partially loaded carbon 748 is less thanthat adsorbed onto third partially loaded carbon 742.

Fourth partially adsorbed rhenium PLS 752 flows from fourth adsorptioncolumn 744 into fifth adsorption column 750 containing strippedactivated carbon 702. Rhenium lean PLS 708 flows away, for example, forother metal recovery. Loaded activated carbon 710 from first adsorptioncolumn 728 flows to an elution vessel 754. Any suitable elution vesselmay be used with the present invention, for example, one or a pluralityof 2600 gallon elution vessels. One skilled in the art will appreciatethat flow through any number of columns, in series, in parallel, or inany other arrangement, is within the scope of this disclosure.

Water 756 and eluate 758 are mixed in mix tank 760 to yield an elutionsolution 712. In an exemplary embodiment, elution solution 712 comprisesone or more of sodium hydroxide, ammonium hydroxide, lithium hydroxide,and potassium hydroxide. Boiler 762 heats water 764 recycled through aplate heat exchanger 766. One or a plurality of heat exchanges can beused. Plate heat exchanger 766 in turn heats elution solution 712 toyield heated elution solution 768, which flows to elution vessel 754. Inan exemplary embodiment, the temperature of elution solution 712 isincreased, for example, to about 100′C to about 140° C., or to about100° C. to about 120° C., or to about 100° C.-110° C.

Spent carbon 770 flows from elution vessel 754 to carbon pre-treatmenttank 772. New carbon 774 is washed with water 776 in wash tank 778 toyield washed carbon 780, which also flows to carbon pre-treatment tank772. Wash 782 with reject fine carbon flows to a carbon super sack 784.Carbon super sack 784 can be drained of excess water 786. Carbon incarbon pre-treatment tank 772 flows through carbon rotary kiln 773 forre-activation of carbon via pumps 775 and 777. In an exemplaryembodiment, carbon rotary kiln 773 is rated at 200 lb/hour. Strippedactivated carbon 702 then flows into fifth adsorption column 750 viapump 779.

A rhenium eluate 781 flows from elution vessel 754, via pump 783, toeluate tank 785, where it is mixed with aqueous solution 788. Anysuitable eluate tank may be used with the present invention, forexample, one or a plurality of 15000 gallon eluate tanks. In anexemplary embodiment, aqueous solution 788 is sulfuric acid. A resultingrhenium rich aqueous eluate 718 flows to a solvent extraction (SX)process tank 790. Any suitable SX process tank 790 may be used with thepresent invention, for example, one or a plurality of 1000 gallon SXprocess tanks.

Rich organic 792 flows to a solvent extraction stripper 794, where it isstripped with a striping solution 796. In an exemplary embodiment,solvent extraction stripper 794 is rated at 20 gal/minute. In anexemplary embodiment, stripping solution 796 is sodium hydroxide. Leanorganic 798 returns to SX process tank 790. A resulting rhenium leanaqueous eluate 724 flows to a raffinate pond or is recycled and reused.Concentrated rhenium 726 is available for storage and use.

Example 1

A stationary phase comprising activated carbon was loaded with rhenium.Three aqueous elution solutions comprised ammonium hydroxide in varyingconcentrations can be prepared (see Table 1). Ammonium hydroxide wasformed by adding ammonia to water. Each elution solution was heated to atemperature of about 108° C. to about 110° C. and passed through thestationary phase at a rate of about 1.5 bed volumes per hour to about2.0 bed volumes per hour. The complete elution cycle was about 4 bedvolumes to about 6 bed volumes, Rhenium can be recovered through theelution and results are shown in Table 1.

TABLE 1 Rhenium Yields at varying Concentrations of Ammonia Eluate Conc.% Re Yield, % NH₃ 0.5 95.2 NH₃ 1.0 95.9 NH₃ 2.5 96.1

Example 2

A stationary phase comprising activated carbon was loaded with rhenium.Eight aqueous elution solutions comprised ammonium hydroxide in varyingconcentrations can be prepared (see Table 2). Ammonium hydroxide wasformed by adding ammonia to water. Each elution solution was heated to atemperature (see Table 2) and passed through the stationary phase at arate of about 1.5 bed volumes per hour to about 2.0 bed volumes perhour. The complete elution cycle was an average of about 16 bed volumes.Rhenium was recovered through the elution and results are shown in Table2.

TABLE 2 Rhenium Yields at varying Concentrations of Ammonia Eluate Conc.% Temp, ° C. Re Yield, % NH₃ 15 22 80.8 NH₃ 15 50 92.0 NH₃ 15 80 91.4NH₃ 29 22 88.1 NH₃ 5 50 88.0 NH₃ 5 75 93.3 NH₃ 5 50 87.2 NH₃ 5 50 89.4

Example 3

A stationary phase comprising activated carbon was loaded with rhenium.Three aqueous elution solutions comprised sodium hydroxide in varyingconcentrations can be prepared (see Table 3). Each elution solution washeated to a temperature of about 108° C. to about 110° C. and passedthrough the stationary phase at a rate of about 1.5 bed volumes per hourto about 2.0 bed volumes per hour. The complete elution cycle was about6 bed volumes to about 8 bed volumes. Rhenium was recovered through theelution and results are shown in Table 3.

TABLE 3 Rhenium Yields at varying Concentrations of Sodium HydroxideEluate Conc. % Re Yield, % NaOH 1.0 98.6 NaOH 2.0 97.1 NaOH 5.0 96.9

Example 4

A stationary phase comprising activated carbon was loaded with rhenium.Eight aqueous elution solutions comprised sodium hydroxide in varyingconcentrations can be prepared (see Table 4). Each elution solution washeated to a temperature (see Table 4) and passed through the stationaryphase at a rate of about 1.5 bed volumes per hour to about 2.0 bedvolumes per hour. The complete elution cycle was an average of 16 bedvolumes. Rhenium was recovered through the elution and results are shownin Table 4,

TABLE 4 Rhenium Yields at varying Concentrations of Sodium HydroxideEluate Conc. % Temp, ° C. Re Yield, % NaOH 15 22 59.0 NaOH 15 50 88.3NaOH 15 80 93.6 NaOH 40 23 69.9 NaOH 40 50 85.3 NaOH 40 50 79.6 NaOH 4050 84.7 NaOH 40 80 89.0

Example 5

A copper heap each solution was contacted with four columns in seriescontaining a stationary phase comprising activated carbon. The copperleach solution contains 0.65 mg/L of dissolved rhenium. Other metals,such as aluminum, cadmium, calcium, cobalt, copper, iron, magnesium,manganese, sodium, nickel, silicon, vanadium, yttrium and zinc, werepresent in the copper leach solution at concentrations greater than theconcentration of dissolved rhenium. The copper leach solution wascontacted with the stationary phase at a rate of 0.125 bed volume perminute for a period of 3 to 4 days. Rhenium was measured in therecovered elution solution exiting each column and results are shown asin Table 5. The average rhenium recovery from the copper leach solutionwas 96%. The average rhenium loading onto the stationary phase in column1 was greater than 2000 mg Re per kg carbon.

TABLE 5 Average Rhenium Concentration of Copper Leach Solution exiting aSeries of Four Activated Carbon Columns Column Rhenium Concentration,mg/L 1 0.314 2 0.155 3 0.072 4 0.025

Finally, as used herein, the terms “comprise”, “comprises”,“comprising”, “having”, “including”, “includes”, or any variationthereof, are intended to reference a non-exclusive inclusion, such thata process, method, article, composition or apparatus that comprises alist of elements does not include only those elements recited, but canalso include other elements not expressly listed and equivalentsinherently known or obvious to those of reasonable skill in the art.Other combinations and/or modifications of structures, arrangements,applications, proportions, elements, materials, or components used inthe practice of the instant invention, in addition to those notspecifically recited, can be varied or otherwise particularly adapted tospecific environments, manufacturing specifications, design parametersor other operating requirements without departing from the scope of theinstant invention and are intended to be included in this disclosure.

Moreover, unless specifically noted, it is the Applicants' intent thatthe words and phrases in the specification and the claims be given thecommonly accepted generic meaning or an ordinary and accustomed meaningused by those of reasonable skill in the applicable arts. In theinstance where these meanings differ, the words and phrases in thespecification and the claims should be given the broadest possible,generic meaning. If it is intended to limit or narrow these meanings,specific, descriptive adjectives will be used. Absent the use of thesespecific adjectives, the words and phrases in the specification and theclaims should be given the broadest possible meaning. If any otherspecial meaning is intended for any word or phrase, the specificationwill clearly state and define the special meaning.

Various embodiments and the examples described herein are exemplary andnot intended to be limiting in describing the full scope of compositionsand methods of this invention. Equivalent changes, modifications andvariations of various embodiments, materials, compositions and methodsmay be made within the scope of the present invention, withsubstantially similar results.

1. A method for recovering rhenium, the method comprising: feeding ametal-bearing leach solution comprising rhenium and copper overactivated carbon to produce a remainder solution; feeding said remaindersolution into an ion exchange to produce an electrowinning solution;recovering copper from the electrowinning solution; and recoveringrhenium from at least one of the activated carbon and the ion exchange.2. The method according to claim 1, wherein the recovering of rheniumfrom the activated carbon further comprises: adsorbing said rhenium ontosaid activated carbon; heating a basic aqueous solution to a temperaturegreater than about 105° C.; and recovering said rhenium by eluting saidrhenium from said activated carbon with said basic aqueous solution. 3.The method according to claim 1, further comprising leaching ametal-bearing material to yield said metal-bearing each solution.
 4. Themethod according to claim 2, wherein said basic aqueous solutioncomprises a hydroxide salt.
 5. The method according to claim 7, whereinsaid hydroxide salt is at least one of sodium hydroxide, ammoniumhydroxide, lithium hydroxide, and potassium hydroxide.
 6. The methodaccording to claim 8, wherein said hydroxide salt is present in saidbasic aqueous solution in an amount from about 0.2% to about 5%.
 7. Themethod according to claim 7, wherein said hydroxide salt is sodiumhydroxide in an amount from about 0.5% to about 2.5%
 8. The methodaccording to claim 1, wherein said leach solution comprises less than 1mg/L rhenium.
 9. The method according to claim 1, wherein said rheniumeluted from said activated carbon is greater than about 95% of rheniumin said metal-bearing leach solution.
 10. The method according to claim1, wherein heating a basic aqueous solution to a temperature greaterthan about 105° C. is to a temperature from about 105° C. to about 115°C.
 11. The method according to claim 1, wherein heating a basic aqueoussolution to a temperature greater than about 105° C. is to a temperaturefrom about 108° C. to about 110° C.